-
uni11o
tl ~ iJ ... .. .. ~-' ... I ... 1 ., a-11 1:nnu'Y1L \Ul'U.~\Uf,fh1n1tlfl111J£ln·Dan~'U.tlfl1~ ') an,ym: fl1~R'l1~LLa: • fl1111Wll~\ufnun'ltlfl1funfl~in n11L1un~£lW11LLfia:ti1:L11'Yl w11Uiin1u111~ n11Lfl1tJ11 n'" ~'"i~ilt~fi1~ 'J "ii1nn1tlfl1fu Elnlian n11LLtJn wa1 u ft'1'l£l'U. vi"U.n'Yln~ittlti1 u,\ ,;A~\~ n1t~ • • • .. ~- u· - ~ ., ... ...1 '1 ..... ~ . I ... I ., T ., ~ ... fl111J elnWJJftn !Jn1tJ1n11LL 'Yl'U.'Yltl1tJ'U.1flft. £) Lnft'Y1~\fLD'l1ft fl1111LLflntl1~fi1'U. Lfl1~W11~'Y11J
~atiafl1111L1fiatl~ffiu1 LLa:tl~ffiu16'U.,£l~£l"'tvi'"1MJ£J~n,.tlfnfunnlftan
1. '41LL'U.nEl"'t~'"1Mtiltlti1~ 'J11El~n1flrnfu£Jn~in LLa:uanfl1111LLtlnth~ti1'U.Lfl7~m~lti ... A ... :T ., ... ~ I .. ~- '1 .,
2. L 1Un~£lLLft:L-n !J'U.~tl'l Lfl1~m1~£l"'t ~'U.1iJJ~tltl1~ ')1J£l~n1flfl111J£lnWJJan Ltl ... .. ...... ... .. . .. ~- _.., ... ~ . ~ .,
3. 1 Lfl71:~ RlllJ fl'Y11~n1 tJ111~,a~ £l"'t~'"lr11£l~n,.ttfl111J~n·Dan lJ"i!"ii tJ'Yl Ln u1-n a~ LLa:
LmuuL fiuul.r
4. L ;j !J'U.U~MtJ1n11Lfl1Ull El"'t ~'U.nLLtla:'JJ\ltl1J£l~n1flfl1f1J£ln~an tJ ~ffiu1 L fl ij~ L ntlrllJ ft'11 I -r tl ~ .. .Y a .... - ..1 A ~ A '1 .,
L~a1'U.LLWfl~ft'1,. 1:nnu'Y1 L"D R1111:1JQn1tJ1 TI1'U.1tJ~fttl~ft'Y1Lnfl Lfl
5. 'l.t1tl~ffitJ1Ltl\fLfl1tJllft'11ti1:L11'Y16~')Lti
CM225 401
-
I , .• •
e-uw~lf,je"n'fltnfuen'iinLiJ~nallw11~ihJ\1iVf"ni\4ill~~fnu uth~:~ilflii~li . . .. . .. tnfuaitarn"WUtr:nue:fl011~R1l1~l~~1ft1JR" L1t-u X, OCOR, OR. LUil: NR2 ft11nallif' .. . ft1lJ11nLfl1u11lti·;nnR11fl'un1Lilfl~iltlLfltl1nu L~annuunwa1uti1uJ,~:llfW11tiurhLilf1 .. L~3Jnaufi-u -uan~1nd'!T" iiwtnJt\Lt1ihLuu~ilu1nu fi a1a"l 1fi a1Jliffiu1nuil1f'l ile l v4tf~ ~~'Dis (acyl ~roup) a~~\4na"n'flf'l1fuan4inilft'n~m:: 1"'"rn",t1lt.1Lilu
:o: II
...,...C,•• R Z ~
acyl group
L~a z = OH tnnh;nou fie n1ttfl1man'iin =X; 'D'itmliiRI (acid halide)
= OCOR (-.,1a Ar); UD'iflUEJU~li1~J1i (acid anhydride) = OR (-.,1a Ar); 'EJttU'IDf (ester) = NH2, NHR, NR2 ; EJ.:~vl {amide)
10.1 · D\\,\\B!ID\1n'1tlA11uunifin (O.arboxylic Acid· Derivatives) ' . ' Duwuha"n1flfl1fuaniin Li1Utf11~Lfl1u11lti~1nn1flfr1fuon4in LLft:LlJ~vu ' niu\ lfn1t'1ti1fu on 'Bin ltitt1 rn.JLin;u1LUJnRft1 uti1 ull1 lfl uiln1fl~1a LU RL iJut11 L i"
~1a l1i£it11L i"nltl' Li1oLmU1JL nuunu lf'l1-3ft"f1", a"n1flfl1fuon4in ~::L ~\411W1\4~LUU OH ,Eh1fl1fl \]flLL't1Uti1U~~LL'YlU~t"ij"~Ul\Ltfuil1t1R1ol~tf \~o~~utfth" ') ti"if'
0 It
R-C-OH Carboxylic acids
402
f;? ' R-C-CI Acid chlorides
0 0 II II J
R-C-0-C-R Acid anhydrides
0 II
R-C-OR Esters
a· " R-C-NHz
,o R-i-8-NHR Amldes
I~ R-1C-NR2
CM225
-
L~Eift'111.h·::nEI1JL\U~1\{~~5h'\liLLnU~ L~'" -X, -OH, -OR LLfl~ -NH2 V\;EI -NHR . . ' V\;EI -NR2 Ln1::rl1J'M~UJWft (RCO-) n1l~ft111Jflfl1~Ltliiti1~'1.J',l10L~EIV\~Vf~ni"U.-n\t~ Lfl£J1n'"d\iJLn1:rl1JV\liLLEiflflfl\'\1EILLEI;R
'U
ca; ca; fi'A. I
-
1 0.2.2 usi~msu llllfl7,{ (Acid anhydrides)
Anhydride V\1J1t.til"thiffi1nJ1 il"t~'"f11itflii'Liifli1nn1flfl1f1Janlian 2la.JL~~~ LiaaJfieH1u19lviin1'nlitnl1aan 1 1aJL~~~ 'V\~Vl"niu,a"ueifl~'DU~lllfl1ffih:na1Jti'1t.t 'V\a.heia 2 'V\a.i ~L~aaJii"nuN1ua:flaaJaan~L1'U
'U 'U
0 0 II r---------- II
R-C-101-:1 + · t1o-c-R1 1 .. .. ·---------- ft~~,o~
acid anhydride ,
UDfflUDU~I1~fl1flij,.f"LL1J1Jft'1J1J1tll 'V\1El simple anhydride ~"U1:nEl1Jti'1t.t'V\a.itDiR 'U
L'V\iJEl'Url'U 2 'V\J.i ('V\1El R = R1) LL~:LLlJlJ~ftlJ (mixed anhydride)~" R LL~: R1 'a.iL'V\iJEl'Url'U 'U . 0.1!!lY.1lf~
A • I II· .I ~ A ... 'I II I ~ simple anhydride •1H1u1:n EllJfl'JtJ'V\~,D·DRL 'V\lJEl'Un'U L 'V\ B1'U-.oEln1tl LL~:LL 'n'U acid
ti'1 tJ anhydride ., ., .. A I ~ I ... 'I II' ... . ~ .. 1 ...
UD U '11 'fl 1flLL1JlJ~ ft'1J 11h1'V\ lJ' D'71Sfl1"n'U L 'V\ El1'U11Bn1fl't1" ft'El"1f'Ufl fl tJ L 1 t.l" 'U
fl11Jft1i1Jen1Y1 LL~:fl11Jti'1t.t anhydride
fi1Th1fl1 0.2 i1mh~n11L';tJn"Difl"DU 1D1fl1ff1.J1'11ttrilfl
iatUPAC
0 0 II II
CH3-C-O-C-CH3 Ethanoic anhydride Acetic anhydride
Propanoic anhydride Propionic anhydride
Butyric formic anhydride Butanoic methanoic anhydride
• 0 0
o-~-o-~:-Q Benzoic anhydride Benzoic anhydride
404
Benzoic hexanoic anhydride Benzoic caproic anhydride
ueif1UDUtl11fJ1l11ittlLU'U1" (cyclic anhydride) ~"1J1i1nn1fl 1fJf11fuDniin liL";t.tnfl11J~a,a"n'",f'"'1 LLft:fi11Jti'1t.t anhydride Liunu
Q Qo ~o 0 0 0
succinic anhydride maleic •nhydride phthalic anhydride
CM225
-
10.2.3 &DW&nDf
LDR'L??DnU\lEl\n~~~f!JEh1n,.flfl1f1Jfln4in ~~~a.j --QH nnU'Yl\ltl1tl -OR ~'iEl -OAr 'I .. ..
lfl,.~trn~-na~La«Lnaf~~iJ~lhaiam~W'untfu -OR ~1a -OAr ..
isoamyl acetate
propyl acetate en&L~~
1 0.2.3.1 !J.?J{tii.TJ.t.El.
0 II
R-C-:OR1
L~El R:: H, alkyl 'VI;El aryl R1 = alkyl 'VI;El aryl
ethyl butyrate i1.Jt.l:1fl
methyl butyrate &LD'l.JLi]R
CCOH
COOCH3 methyl salicylate
'u1al'u1:rh
n1,.L1tJnLElRL'YlElfflR1tln1,.L1tJnLnftEl11El~n,.flfl1f1JEln.fin· ltltJL1tJnLU\l ~fl
-
r,1-3m-3 is /URAC fsruiw 0 II Methyl ~ethanoate Methyl acetate
CHs-C-0-CHs
1?-o CH3CH2-c-o . ~ b . Phenyl• propanoate Phenyl propionate 0 II Butyl methanoate Butyl formate
H-c-0-CH2CH2CH2CH3
0 II
Isoamyl acetate CH3-c-0-CH2CH2CHCHs 3-Methylbutyl ethanoate CHs
0 II
CH3-CH-C-O-CHs I Methyl 2-methylpropanoate Methyl lsobutyrate CHs
0 o-c-0-CH2CH2CHs Propylbenzenecanoe~ate n-Propyl benzoate.
o-0 8-0-yH·CH3 Isopropyl benzenecarboxylate Isopropyl benzoate CHs
1 o.2.a.2 J!ft~fJJJH!tn~fJUf~!11!11P.n.f.~
Ulft'Lnaf-nilfl1~LL'V\1U (cyclic estet~ 'V\;a~~-~.aJ.riY. (lactone) Lnfl~1nu~ffit111l1Vtu
1aJLftnft~El~n1f1JllfJ1Dn4f (hydr~xy acid) 1flt1L~Vn:~ii -OH au\U.,1LL'V\\4~LLn11111 (y) LLft: . ,.. 'f1ftf11 (8) ~a~'V\litnfuan'Ba . ,..
406
~ HO-CH2CH2CH2-C-OH .... 6
(cyclic ester)
d TI1!(i~n.~!.~ft!1~.~-'-4r.t~f. forurtyL;unLilu lactone
~1nfo'Mft'n~a~ntt1 LL'YIU -ic atr:id tuton1tltl1tl -o/acton~:
~U1t11~LL'V\1Url1'V\Utlltlvan~m1nt11li.,,LL'V\\4~tnfuou~Ln1:riu -0- tu1~ L-rlu p, y ~a: 0-actone LUU1.JLalm'Yiof!Ju1t1 4, 5 u.a: 6 o:tloaJ fl11J~1tiu
CM225
-
Butyric acid P-Butyrolactone
Butyric acid y-Butyrolactone
Valerie acid y-Valerolactone
a600 P a
Valerie acid 5-Valerolactone
y
uJo P4cH y . 3,
Caproic acid 5-Caprolactone
10.2.4 stlJJff (Amides)
D~~J.Jtl LU'Utel'Ut~'UtMJEl~fl1tlfl1ftJan~an ~~'V\3.i OH nnLL'YI'Uttl1tl NH2 'V\;El NHR 'V\;El 1 ~ ~ NR2 LLt.i~tl1llfl11U.'YI'Ut~~l'Ut1fi1L-;J'UtLU'Ut8~~11ff1J~ll1lD D~~JJl'YitltJ1lli LLft::D~~JJffflflt11lD ij .. .. 1 ~ ~ ~'Utlr:: N-C '41'Ut 1'Ut 1, 2 LLft:: 3 ~'UtCtl1ll~1tltJ
0 It
R-C-NH2
~ R-C-NHR Amldes
0 II
R-C-NR2
Li1a R = alkyl ,.,;El aryl
l 'Ut 1 fi1L -;J 'Ut L 'UtD ~ ~V fl,li ii ft'll Ui L iJ 'UtL 1.J ft' L Y411::fi·a Lin tl1 El 'Ut 1 fl fl L ~ tl1 L fl fl L 11 'lJ LL 'Ut 'Ut.f ~
LfliaOUtl1JLOUt1fl1~Ri1~lt1
CM225 407
-
10.2.4.1 .TJ.J.!(f.!I.TJ'!.EJ.
LtJiu-u ic acid ~;a oic acid ~1nian'l'tlfl1fuan'Bfin Li~J-u amide 'f ... .J.. .J.J ~~ ~I .. ... I"" ~ I ...~~ _,
D~ UJflfUJn11LL 't1'U 't1't1 N L ~ D1'ULLUU Lfl tl1n'U LL911J'Utl1 tl~ll LL 't1'U 't1'Jh1 L n1:nu N '1.1
I ~ I~ 1 I iJ .J.J iJ I iJ .. D1'U1JD~~'U'U-.J tlti1:~11L 'l.L011LL't1'U't1't1 N L 'U D'l'UL 'U N-alkyl ~'l'El N-aryl • ~ ~ ., ... .J
na-u LLft:tl1lltl1ti1JDD:- '11fl't1111~1nn'l'tl
fDIUPAC
Ethanamide Acetamide
Butanamlde Butyramide
9 H-C-NHCH~H3
N-Ethytmethanamtde N-Ethylformamide
0
)lN~
6
408
N,N-Dimethytmethanamide
N-Phenyi-N-propytethanamlde
N-Ethyi-N,2-dim(:ttli'lylpropanamide
2-Ethyl-3-methytpentanamlde
N,N-Oirnethylcyclopenrboxamide
N,N-Dimethylbe~mlde
N,N-Dimethylformamide
N-Phenyi-N-propylacetamide
N-Ethyi-N-methylisobutyramide
a-Ethyt-{3-methylvaleramide
N,N-Dimethylbenzamide
CM225
-
1 0.2.4.2 .l~ft~!J.fJ.;.l~.{~H!~r!1!~iP.tJ.f.f! a:~vl1filfi1~LL'V\1'U. (cyclic amide) L1vn .L!~!J.L}.r!~ (lactam) Lnfl';l1ntl~mv1l'"
1liLanaLtl!J1tl14 1:'V\11~'V\1i -NH2 LLa: -C00H ttl\l1fiiJJ£J~1~\u1:1J1Jtnajruf11'V\14fiLL1J1JLtl!J1tl1J ~ ~ w LBft'LriBnUfli.JLLVIIU LLfiL1!JnLU'U. lactam L~'"
0
. a.ANH
llY' CH3
rJ-butyrolactam
10.2.5 luln,-if (Nitriles)
a)NH rJU8
y s
e-caprolactam
J.~lr!1; .(R-CN 'V\;EJ ArCN) ii'V\~?f~ni"U. -C=N ~~ti1~';11n£J't~'"f,.t1Ltl-na~n1fl fnfuan~an Lii'U.lfl1~iifl11llill~uilflve1'a1lnua:wl ';)1~n11LivJ,-na~a:wltl13J1lii ... ~
• I"" - 'f 'f _, ., .- =."" ..,. .-..I .I ... 'f 'f .- •-I lJL)n1v1-na~ ,u '"'1R fla1vn1ttfl11U£Jn·JJanLLa:a't~'"1l£J'U.') n11'Yl';lfl '"' '"'1R£J~ L'U.
I .I ... • ... .. .. ...... ., ..I nalllfl1lJ1:n auLa'lfR'V\1£1 au ~'UlliJJ a~n1flfl111J an-uantt1 v L 14£J~';l1n ~ ~
1. ~tl1'U.:aan~Lfl-i'U.-n£J~fl1fua'"l'""'li -e=N Lii'U. +3 L Yhnufl1fua'"~"'lifl1f ~ ~
uaila 'V\;a,aiR 1 l"U.a14~14fl1a~n1ttfl1fuan~an ~
2. fl1fua'"~"'li -e=N ij~UiL'V\ila14fl1fua'"-na~'V\liLaiR fiarhtJnn~hnnuil1f'1a ~ ~ :..1
la L ~a1iLL1J1J_Lii !J1tl'U.
3. nnLtr1fi1Ltufl~ntflflTf1Jan•anL~'"n'" ~
... ..I 10.2.s.1 DJ.1.~1.~.n~.rJ.
~;~!J .. HJ.P-~.9. L1!Jnfi13Jan~m:n11LL 'YI'\4 ~Ltf 1tt1L ';1\LIJJ£)~ 1fl1~ rn~'V\ an .r~d
"'1l'li"'an ~ii"'li eN ~
~1'"1'U.fl1fua'"l'"1fl1~m~"'anll'u113Jfl1fu£J'U.-n£J~ eN ti1v
a~'ri1!J~EILtr1fl1fl1fua'U.~Lii'U.1fl1~rl1~'V\ant11!J -nitrile L1vnLiJ'U. alkanenitrile, alkenenitrile 'V\;EJ alkynenitrile LLa1LLtin1m
fl1fuawtm~ CN Lil14fi1LL'V\\i~~· 1 Lliti£J~1:uLa-nfi1LL'V\1-i~l'"~a ~
CM225 409
-
.n:n:~!P.n!lJ.~1JJ;:~!.lnro1 L1vnLih~ alkyl cyanide
~;£lft-\Jli'1Vtl1V -carbonitrile L~O~ai -CN Ln1:~1-\JLL~1'U . 'U
~-~.'-J.~Jll L1vnfl11Jn1flfnfuen4Bnn lflvLl.Jiv" -ic acid li'1v~en1fl LU'U -onitrile
ethane nitrile 'M;O
acetonitrile
~~N 6
5 4 2
5-methylhexan•nltrile 'M;B
4-methylpen~l cyanide
cyclopentanecarbonitrile
'M;O cyclopentyl cyanide
Q-c=N benzonitrile
Q-cH;zCE:N phenylethanenitrile
'M;B phenylacetonltrile
~-10.3 ftiJ1Jtlfl1\1fl1fJ111ft
LL1-\11:~11-\J 111Lftnft~El-\JEl'U~'UfuEl-\Jn'Jflfl1f1JDn'BnnLiJ'ULL1-\11:~11-\Jlfll Wft lfiVL\\?41: • • •
D:'~11~1.Jt1JTiiiLLft:flfiVTiiilS-\Jii~'Ulr.: N-H '11'U1'U 2 US: 1 ~'UlJ: n1l~Lfifl~'UCltrlfl1L';l'U • 'U • 'U
1:,.,11-\1 l1JLftn a ~-\Jij';) fl~SEllJL ,_,S1LLS:';lflLtlflflft'-\Jn11811~'U ,.t1 l1.J~U1~\l'n 11JLSn SL ti1 ')n'U • • • 'U . •
lfl v L\\ w1:a:-~vll.J:ilJTI iitS"~"';)fl~ a ElliL ~ s1"a:';l fiLtl Elflft'-\Jn11n1flfnfu an•n n 81~ ruD:-~vl ..; 'U • • 'U
- ... -~ " " !M ~ I .. - J! ~ ~ ...... ....f ~~.. .. flflVTI11LLS:ft'l~lJ1:nau 'u '"1SJJft'm'Vftl1fl ElU111-\Jft'-\JUJElLTtVUnue'U V-4'UD'El'U ') r11 L~';lflLfl Elfi&N
'U 'U • • 'U
L-D"n"
410 CM225
-
.. ., .. - - ., ., .. - i1 ... .J r ... .., ::. ""· ~ LEJft'Lt1EJ1, EJ:' UJfl'Yiflli1UJ LLa: UUt11fi1J1~~'"fl L '"fi1T11ft:ft1ti&EJ W1flnV"I'Yifl L-D'" ~ v .
ethyl acetate, dimethylformamide (DMF) LLR: ~nitrile
alp~''"f-na~n,.flfl1f1Jan~anw1'"\~qtftijfl1f1Ja'"'~Ln'" 5 a:flalJ s:a1uJ1Liia~·;nn Lflfl~'"1f:,ULfl1L,-,'"n1JJ1'~ ff~\fi~'\t1J1111UEJifJflREJ~1flLLa:LLEJU~l1~fl1fl;A~'1flEltl~n1tJ1tl1J "' (( \bLLR:LLaanEltiElR
.. ,,";t 10.& LmuuLiluuthfl~ftn,~n1ll1l1~~o~n~flflTfuon~anuft:au~ul ua:ft1,.th:nou tJ1~~uflftiiJ,"',rn ta.nana \niLf\u~nu ~ •
WUC',IJlfl1LiU • rf)1"rn" l..f1~LnYIB11 uu. YflLflDfl n11R~R1t.1J'1 TJJLRnR 1~wi1" TJJLRnR (c~ . •
CH3(CH2hCOOH .. ... ...
88 ...
164 ... n1tlfl1,.tJ £m'Jfan 11 tlll1n
CH3(CH2)2CONH2 a: '11 lt1•11nii 87 ....
216-220 a::a1vttr lJ • 'II
CH3CH2CONHCH3 \lJ.. ... ... 87 ... 205-210 a::a1vttr a: fl'YltllllllJ lJ • 'II
CH3CON(CH3)2 ' .. ... ... 87 '~ii 166 ... a: lJfl9l9llltllJ tlll1n 'II HCON(CH3)CH2CH3 a: 'lJ titl ilunii 87 '~ii 170-180
... tlll1n 'II
CH3(CH2hCEN ''"'n,.a- 83 ~ii 141 . ...
Lan'"av
HC02COCH3 LLa~fl LL£lU 't'J'tl,.t)' 88 ' .... . lJlJ 105-112 orhtJ~ffirnnuJ1 CH3CH2C02CH3
.. 88 '~ii 80
. ... L £l ftL 'Yl 0,. Lan'"av CH3C02C2H5
.. 88 '~ii 77 t.h'"na1.:1 L£l m 'Yl a,.
CH3CH2COCI ... ' .. LL£l'Jftlflaa ,.tl 92.5 '~ii 80 n1tJ~ffirnnuJ, CH3(CH2)3CHO , uaail,ul 86 ~ii 103 •
... Lan'"ev
CH3(CH2)2COCH3 f\tnu 86 'liii 102 • ...
Lan'"av
CM225 411
-
~a :Q:J
I.e' •• R-c-z . I~
Nu
.•• :o
II ,.....c, .+ r R Nu
Z = leaving group; Nu = il'lflRln,vhf
10A.2 .. ~, ... l-n.Jfimu1!1o"o'tft'"tfmo"n,.tttt1i'uonian
fl11lll 111Eh'lll~ffitn("nul-11i z ~-3SiJ.Jafien..J~ffiv1R£h'ILL1J1J .r"d' "\
.~., · - • ~ 1w .. 1 0.4.2.1 !1.~1l!J~.?..t!~.~f1Jf{).!.ff!J.'JiJ1!~! ..... ~
l"a"~"i'-na-3n1t1fl1fuan~~n z a'l-;,-;,:LiJ'U LLD1RL-;J'U, o -na-3£DBU?Df LLa:uaifl "
uau1111,,; LLa: N L'Ua:-1111 4"£ifiaLanfl1a'Ult1t1L~!.I1Yhl~l-11ifl1fua\ta£iLwflv1n1w
: D:-111{
1 0.4.2.2 .f!.3J.Y]1!!J~.l!J.tAY.{IJ9.9t9.'!P..
Leaving group ~fll-1RfiJ1tJ 1ufiaLShfl1a.'Ult1fi~R:LiJUL1Jft'ela'U LslaLtntJULfltJUn11 " v .
~II A ... 1 "··' .. ~ I ~ .. ~- . ~ .. .. I LL't1'U't1fl1tJ'U1fiR a LnR't1\-13J£D"'llnEl-3n1flfi11UEln~anLLR::ft11a'UW'U1r ';Jt(\-1'U11ft'1l1WL1Jcntel-3 v "
• :'1 ~ ,¥ leavmg group LlJ'Ut1-3'U
1'1l1ViL1JI'
ft e_......c, e e < 0 . R < OR1 Tl1flf11WDnfan > D:-J11/
412 CM225
-
t.l .. t.l I .~ ~ ~ ~ ~.,_ 10.4.3 n11'L Rti\UL a"-stM~1"nM!ID"OMWM6\l1nn'lflft1"SUDn'Dan • (lnterconversion of Acid ~es)
Liia~-;nnalt~\uf~a~n1tlfl1f1Jent&njjfl1111l1t1~n1u1ti1.:niu alt~un~~l1tia tJ~mu11nnn11~~LtJ~uu1.~alt~ufrll1tietJ~mmll'aun11lt1 LLa:'ln~itflvhtJ~ffiu1ntJtl1 ~;annlDLtl1lad\~n1tlfl1ftJan~in . ' .
-
I
CM225
-
NH3 ,.;u RNH.2_
111; 0 R2NH
acid anhydride
carboxylic acid
ester
413
-
10.4.4.1 y_D_ryj_lJ.J.ffJ..M'.~!!.'if]#.~H.~~-~~J:~
"D'ifl"tJ~al fhtJ~ffiu1nuntflfnfu an'i~n ,.,;a Lni a-n a"n1flfnfu an'i~n laj.;' a" 'l " ... • If "' f'l ,.J.. .. • ,. - .. ., -"" • ... ,.J - t¥ L41Jff11L1" LVi11:::"1J 'Sf) 'DDDULu14 leaving group 'Ylfl L14uLJn1EJ13J 'W1flUL~a-;,tJn1fi'YILnf11J14
acid, chforide
0 II
0 g pyridine._ R( 'oH carboxylic acid
0
acid anhydride
0 0 ' c +
CHf 'c1 "-Q Na•-oc ~ A ~ II 11-o CH3-c-o-c ~ !J + NaCI acetyl chloride acetic benzoic anhydride
0 II
- 0 H 0 0
CH3(CH2)s-C-c1 + HO-C-(CHvsGH3 pyridine • C.H3(CHvs-C-O-C-(CHvsCH3
414
heptanoyl chloride heptanoic acid heptanoic anhydride
u·- m., .. 10.4.4.2 · ... D.Q.1.lJ.!..!l •• MJ.~'-~!1P.l UEU~naDaR'VI1aw14aft LiJ14il1flRlalv.JlfLi1n1tJ~ffiEJ1n1JLLa~f1LLlflfttf lt1Laft'L 'Yiaf
0 0 II •• ~ridine II c + HO-R .. I c + HCI
R/ 'ct •• 1 R~ 'oR1 acid chloride
.!T:u:J~J~l-Jjjm!.JJ. 0 II O"C'CI 0 II
CH3CH{"C'CI
propanoyl chloride
+
alcohol ester
pyridine (CH3)3COH · ._
ten-butyl alcohol
ten-butyl benzoate
0 pyridine .. g n +
CH3CH{" '0/--'
cyclobutanol cyclobl.ityl propanoate
HCI
HCI
CM225
-
0 II . c +
R,....... 'ca •• NH3
ammonia
0 II •• /c,. +
R Cl R2NH
2° amine
.!i1tl~J~'='~mP.J. 0
~CI hexanoyl chloride
stearoyl chloride
o-9 C-CI + piperidine
1° amide
HCI
I RNH2 ~ R~H3C~
0
~NH2 + hexanamide
0 II
C H ,...,c,N ... CH3 + 17 35 . I _
H N-methylstearamide
0 NaOH ., Q-8-NJ + NaCI
1 0.4.5 t.lfi M!J1!1il\1UBWfJUBHliJ y,,., Lft ufi'1 lutl~mtl1~ Eh1UDifJUDU tlitfJ1iflR1UntJUDifJUIJtsl fi eni1U~ffit11ntJ\t 1t1S
1a l ~a &t1oul'V\ qjl.,ulliti a~ liti1L i~tl~mr.n LLtit111aJl1u~ffiu111'aun11ue~fJu11~sl.
0 0 II II C C + H-Nu
R/ 'o/ 'R ••
CM225
.. 0 II c
R/ 'Nu +
415
-
uDiflUDU t,tfl1lla.ili'Lfl'iulluDif1flflD t,-l Lrta"~nn leaving group (RCOO- ) LiJ'U LlJMLrifli1 C( ~"'VIftfltnnni1 •
1r .. - m-- .. 1 0.4.5.1 .. !ll.TJ.1.11.1.r! • .'J!d.lJJ!.ffl.FJ.1. UDiflUDU tlT tfl1fffl1t.J ~ fl; U1 n 1) LL a Rna lJ £J a 'VI1 a~ 'U £J R £i fl1 f11 D ni' fl fl tD D D U
(RCOO-) Li]'U leaving group l1-tL£Jft'Lflaf ·
.. + H-OR ••
acetic anhydride
acetic anhydride salicylic acid
cQO
0 HO~
. 0
· propan-1-ol
phthalic anhydride
10.4.5.2 JJ.D.QJ.I/J.~.M'.EJ;.~~~
•
0 II c
R/ 'oR ester
COOH
+
~ &o'c~o , I · CH3
acetylsalicylic acid (aspirin)
Lil~t.Jilmv1nu NH3 'VI~aD:-iiu VuRtlilmu,uuuLilu1nuuDiflu11tt~l fi1"n~~ leaving group LiJ~tnfvsnfu~fl1BBBU 4"Ld£JLOtlUQM!J1tlUNH3 'VI1£JB:iiu1::ltl'LnR£J
0
~ R-H-NH2 + RCoo- NH.t +
416' CM225
-
.fT:HJ~J~,)~fJl'JJ.
0 0 0 II II II
H3C/c,
0/c'CH
3 + 2 NH3 __..., H3C-C-NH2
acetamide
00, 0-o-cll c
11 H N-o-~ CH(CH ) pyridine.., H3c-c11-o ~-~~ CH.(CH3)2 / ' / ' + 2 32 H3C 0 CH3 - .
......... .. 10~4.6 u!J n"IU1!10"&Bif&fJB1
11 .. - m ~ ~ 1 0.4.6.1 .. {l).TJ.1llJ.rl .. Y!tFJ.~~rJ.FJ.1. tl~mtnii'tia n11u.JRuuLEHJU1Df ~;a transesterification Lil14tl~ffirnn11LL'Yl~~~
~ajLa:Ua~a-3LDBL nDf fl'1uu~an at~aaan~\t"~\1-3 t ~Latn, af~\t" t~a.i Lil~nTnll; u~~a.i ~ . ~
R1 L~L£lftL'Yl£lfL~11 nu~a.i R2 ·;nnLLaanaDaftl~aj 1fluiin1fl~LL~-3 L~~ H2S04 ~;£) HCI(g) ~
'V\;£lLtJRLLEJSfJEJn!'lfff (RO-) Lil~tl'1Li-3
.!11!J.~J~Y~m.'J.'J. 0
~OCH3 + HO~ methyl acrylate t;lutan-1-ol
methyl benzoate
· o a· o- 11-o-11--o o-c ~ 11 c-o dicyclobutyl terephthalate
HCI
...
0
~ ~+ CH30H 0 butyl acrylate
cyclopentyl benzoate
diethyl terephthalate
10.4.6.2 !!nffl.~.rl~l~P.;'.~~?f (Amin~lysis of Esters)
LDBLnDi'bfi atl~ffiu1\l'auni1LLDifJLur!sl ua:uDifJuEJu !a!fJ,.; uc;i.Yhtl~mu1n~ LL£l11111LittJ'V\;£lEJ~iiuLtlEJ~!vff L~~n~
CM225 417
-
0 II ••
R-C-OR1 + NH3 0 II
R-C-NH2 + H-OR1
.II 1-\' 0 • 0 ... . " .. 0 '0 1f_. .. .I ... WD'"D 1 'M10 2 D:IJU LLYI14 NHs 1:: Lfl 2 LL&:: 3 D: Wfl tni.Jat1fl1J
.!T:uuJJ:'l1Jjjffi!IJ. 0 .
Q-cH:z8-ocH2CH3 + NH3 . 0 .. Q-cH:z8-NH2 +
ethyl phenylacetate phenylacetamide
0
CH3CH20H
.. . II H-o FCH2-c-N . + CH3CH20H A
N-cyclo~exyi -2-fluoroacetamide
10.4.7 t.lfimEntJINS~W,(
s:~umiJua't~'"~'si•~~1tien.J~mu1\l'au~~" LLfiLntltl~ffiu1n11LLEJnwtnut1'1u LLDRnDDOS (alcoholysis of amides) L\fLDRLYlQf1tl tl~ffimiin1flflLL\f" L~\1. HCI(g) 'V\;D ~04 1iJui1Li" lflutio"t\ffl11~i'auua::liL1R1~1u Li1a"\l1nff"s:~umLa::uoanouosLi1uaLin. T :-1 •• 1 .- ..,. .-T 111 •• 1 .-.1 • ~ .., ~ • ~fl1 LnftLLR::\1.1fla LD LnaYlO£l'U.fl1EJn'U.Yl"fl ..
0 o-Il CH3CH20H C-N(CH3)2 H~O,. N,N-dimethylcyclopentane
carboxamide
+
e~hyl cyclopentanecarboxylate
10.4.8 n111at .. ,laafo'twwf!lo\1n1~tni'uanian
tl~ffiu1il'LiJun11LLunwa1ua't~'"na"n'"fl1f1Jen•int1•uJ,.t"Liluil•flalol~a ~LiJuna1" H20 Li1~1tl1iffiu1~fl1f1Jou-nth1'V\ahsf• ua::ou~ufYln1fitflnnlulfl1lai'l~ w .. .. " .. 01flfl1f1J an 'Bin
1 o.4.8.1 .m!l'-T.fl!l«l.i!fl~!l~!!.llfi
LiJUn11LLYlUflfl1"'Vl1J&sfai1lJ\l1ffLiJUi11flRlal~L(ftLfJuna1" UBfflui'~Blflii . .. . J,Mtl'nlliLRflR~1~1tl~mr.nl~n1tttnftJentinltl'L;1llltia"l-it11Li-a, ~1nftJ,Mtl'nlliLafla ""'::l1ti otl~mm\l'oun11 tlMiiJtl~fflu1ft'n" \ uL1Jft!11t1snt.,.r (HO -> f-aLilu il1t1ale .. . . l ~~~ LL '" tl~ffiEJ1\l::L n4uu:: LiLnRD-nD-3n1f\tnfuon4in
418 CM225
-
0 II
R-C-CI +
acid chloride
0
Ar-8-ct +
acid chloride
H20
,r,
H20
\1'1
0 II
---~•~ R-C-OH + H-CI
carboxylic acid hydrogen chloride
0 . 0 NaOH.. Ar-8-o-Na+ ~ Ar-8-oH
carboxylate salt
0 Q-cH)\-CI + H~
0 Q-c~8-0H + H-CI
phenylacetyl chloride phenylacetic acid
0
Q-H-c1 0 0
:~.r Q-H-o-Na• ~ Q-H-oH sodium benzoate
1 o.4.a.2 .O.?!l'-T.~!l@f.~P.!!!~!R.~J.v.J.~!ff
n11LLtln"a1uusi~JusuYrTYfl,.,r tt1tl,i',l,.;'n1t~fnfuontin 2LaJLafla LLa:~atJ~mu1 '11n t~flinusu Yl1Yfl1llt1n1tl t~Jf'nfusniin tJ~mti1Lnfl lt~ulliti o"lii1Li" usiflusu Y11 y,,.,r~,i','V\\l'n L11Lafl a\1"'1: l1ti etJ~mm\toua" LLa:n1iin1t1LiJ~i1L i"tJ~ffim'l:Ln fiL ;,;f~ ·
ft ft ft ft C C + H20 ... C + C
R/ 'o/ 'R R/ 'oH HO/ 'R acid anhydride
..
cyclic anhydride
carboxylic acid
¢:: 0
dic8rbo)(ylic acid
carboxylic icid
.!T.1fJ.~J~1-J~m.FJJ. 0 0 II II c c
H3C/ •'o/ 'cH2CH3
acid anhydride ·
CM225
0 II c
HO/ 'cH2CH3
propionic acid
419
-
Q+ 0
succinic anhydride
1 o.4.a.a .tJJ.!Iv.f.fJ.!II!mf!!!.U1!!.f
¢: 0
succinic acid
· n11ltJ 1fl1lSRlDRl nDnflfli1 tJ~ffitJ1LflflltiLil Ell ifl113Ji'El'U '1fl !JUfl1fi~1ElL1J RL iJu fl1 L i"tJ~ffit11 ltin1flfl1f1J Eln,nn~1Elfl1flJ Eln,Lftfl lEJElEl'U LLS:LLElftnEltiElft'~1El~'UElft
0 0 0 II H-OH II II
R-C-OR1 R-C-OH "'1e R-e-o- + H-OR1 H• "';u,. Ho-ester carboxylic acid
\14ntfl
.YT:ut~J~!llim.FJJ. 0 II H2S04
CH3-C-OCH2CH3 + H20
ethyl acetate
0 0 .
carboxylate ion
\14UJI
0
CH3-H-oH + HOCH2CH3
(CH3)2CH,0~0 ... CH(CH~2 o~ o HO~OH
diisopropyl pimelate heptanedioic acid +
2 (CH3)2CH-OH
tl~ffitt1~iiL1JSLiJui1Li" L';vn saponificat!on (JJ1~10il1Wlft:ilu: ~3J1E.Jn" soap making ~1Eln11f11SU) liLlJS 11aJft tlElLElBLYlElfLLfift:13Jft 1fltttlJJl-ua!uifl{~1all13JU~11 .. lur11a:a1vLusLLri (NaoH ~;El KOH) HO Liluil1flalalwa~iiL-i1n1tJ~mv1~fl1fuEJu -nEJ"~llmfuEJ\ta ltifiufi l~ 9U4"Lilt4LnREJ-uEJ~n1fl l-uJu. 41"Lilun1flfl1fuEJnlinn l'lim1 .. ' ..
0
o-Na• sodium dodecanoate
1 o.4.a.4 n1!7!!.Tt!!7J!.tf.ll~Jy_fl'
D= ~11~ LiJUEl't~UnEJ"n1~fl1fu&n4fln~1 El'"l1fi otJ~MU1\\'El tJ~ ~fl. ~~ mU1Lflfllti ti1jjn1fl~1EJLumiJui1L i"
420 OM225
-
0 II
R-C-NR2
.!T:u.t~J~1:l~m1:1J. 0 II H-o
CH3-C-:-N ~ !J
N-phenylacetamide
,(
~~. ~oi( 1.~ 'o
0 H+ II
::--;..,;,._~..,• R-C-OH + H ·~ R-N-H
Carboxylic acid
0 II _e
R-C-0
I R
mloLLoaJ tan iluaJ 'M~o mloo:ilu
H + R-N
R carboxylate ion LLDJJlaJLilU
'M~O o:ilu
L~El R = H ..,;El alkyl ..,;El aryl
0 II
+ H20 NaOH .. CH3-c-o- Na• + H2N~
b. sodium acetate aniline
~OH ~o· + HO[f' + ·/""N~ .. I~ 0 H 1 o.4.8.5 m!l'!.Ifl!ltj.tf(f}.~f!Y.~YJn1.l (~1-n a 9.5.4 >
n11lu lt11ltuftu 1fl,.,( (R-C=N) Lil~tl~ffitnllin1~nau tl~ffitnLntl ~1~D: 111ff\~ ·R1l11::n1fl \,.; n1tlfnfuan'iinLLa::LLalJ 1lll \hJlllaaa~ R1~1'1l11::Lua-lti f)1fvDnilsfJ 1DDDU
LLa::LLalJ 1aJL itu
CM225
R-C:N 'M~o Ar-C:N
CH3(CH2)9CN
undecanenitrlle
1. H20, KOH fl11JJiau 2.H+
R-COOH "~o Ar-COOH
+ NH.-+
R-cocf "~o Ar-co&
CH3(CH2)gCOOH
undecanolc acid
421
-
t.l """ ... -· ~ " .. ~ 1 0.5.1 lJn"S!11nlJ81"1u"S=notJLRM=BM't1"S!J
u·- lB t ~II; n1 fl .. • ~ 1 0.5.1.1 . .'Jl!11Y11!fl~Hfl ... ~~ftfl . .1!J.T.U!!!'J .•.. l;.TJ.~'d .. tj.M~(J.M1'J.!I!. EJEJf"n f U"flfU£illV LLR:ns"vu1,Ell iU{fi11J~fl;u1n1JUEJfflflSEJ t 1/ ltl'~f J?U
(i1iD 8.4.8)
1 0.5.1.2 !/.Dfii.t[J'!!.IJ:~~!l.'f}JlP.fff.ll.trJW~flY.fHYJ~~H.~if. ci1io 6.5.5.3)
lEJR,nEJfua.:Jn1flviDfiin ..,;oLon-L n$f.no.:Jn'Jflf11fuonliin~u Yi11J~mu1nun1m1f ;,EJ,iUff 2L11ft fl111tl1Un11lD1fl1lRLf-ltiLLDftnDDOa'Yltl!Jilij 'Vl;DflflU115i~ii'Vlli R L'Vliiounu ············· ' " ... ... ... WO.:J'Vlli ...
0' II
H-C-0-R + 2 R'-MgBr ethef ..
LBI'Lnaf!Ja~ formic acid
0 II
R-C-0-R" + 2 R'-MgBr
LDI'L nof!l~n,flmftJon•ino14, I
OH I
R-C-R' . I
R' 3° alcohol
OH I /
H-C-R' + ROMgBr I R'
+ HOMgBr
+ R"OMgBr + HOMgBr
EJEJf"n Tui' ntJV";l;l1ti otJ~n;U1lnnn1~n1w1n'EJ' vul Ldon11J ~n;u,~: 1 ~ LLDRnDtJOa'YltlUilii 'Vl;DfltlUilDL'liYLtlt.l1nY " ... ...
0 II
R-C-0-R" + R'-Li
n1ty1n'EJ' vul uR:sEJfun Tui,ntJutl1tJ~mu1nu'Vl~ ...;.caN ~~tl o111\ln lu lt11lR Lf oth.:J11flL11lti~fnu .
422 CM225
-
nitrile
R\ 1Mgl
H20~ ~ c=N
I •• R
~+ ~-
R-c=N + R'-MgX ---1..,..
.!T:u:t~J~,)~f)1FJJ.
Q-c-N + CH3Mgl
benzonitrile
H3c, ,Mgt ---~....... c=N d ..
R' H R' 'c=N' H o• \ 3 ~ c=o I .• r{ R imine ketone
acetophenone
... - .. .. .e• ... .. .. -- - - ., .. UAJH4 1fl1Rn'l'tlfl11tJEJn·Danua:a14~141MJEJ-3n1flfl11tJEln'lfannni!Jf14fl LLEJ!IflfiREJ ,1, ' '
LLEJ'ifiLLEJU !a~f11ff LLa~LEJft'L rJEJf nn1ti1tfl~LLElROEJlf£la'lht1111 ij ft114D: !11/ LLR: ~ U! r11R';l: Ltl ~ Q ~
R11th:naue:ii14
Ql~~lj (diisobutyl aluminum hydride) LU'\4ft1nii1wtA-3l1'll'auni1 LiAIH4 tn1111tl ..... .. .. ~ .. .. iJ ... , .. ... ~ 1f11RLLD'lfflflREJ 1fl LLR:L£lRL'YlEl1L 14LLEJRfl lffl ('V\1~£) 8.4.8)
0 H II LiAIH4 H o• . J R-C-OH 3 ~ R-C-OH + H20 ether I
H carboxylic acid 1° alcohol
0 H II LiAIH4 H o• I R-C-CI 3 ~ R-C-OH + ·Hct ether I
H acid chloride 1° alcohol
0 0 H II II LiAIH4 H o• I R-C-0-C-R
ether 3 .. R-C-OH + H20
I H
carboxylic acid .1° alcohol
0 H ll liAIH4 HaO+ I R-C-OR'
ether .. R-C-OH + R'OH
I H
ester 1° alcohol
0 0 II DIBAH H o• II
R-C-OR' toluene
3 ~ R-C-H + R'OH
-70°C ester aldehyde
CM225 423
-
·.tl1tt~.1~1J~fJl!JJ. 0 II
~CH2-C-OCH~H3
LIAIH.4 .... H o• 3 ... ~
ethyl phenylacetate
~ ~CH2~C-OCH2CH3 DIBAH
V toluene · -700C
H o• ~
0 " .. ... _til Ill 0 .. 1 B~ UJfl fl01tl1ftL" 1 8~1/U .,
octanamlde
LIAfi.t. ~
N,N-dlmethylbenzamlde
10.5.2.2 OJnft1!r1YJr.t!l,
~CH2-CH2-0H
~ +. CH3CH20H
2-phenylethanol
0 II
~CH2-C-H + CH3CH20H
.
2-phenytacetaldehyde
H~ ~
~NH2 octan-1-,mlne
CH3-CH2-NH-o
N-ethylbenzenamine
(~amine)
N,N-dimethylbenzylamlne (3° amine)
YuYrnl an1il1ll~ 1°EJ:uu Jl1a1Laa~lutf ;f"ntmil9rllfl-311nil1lf Lda\,Y LiAIH4 1t ., . ltl'1° B~iiu LLthi1;il1ft1'1EJ DIBAH 1::ltiuaaifllmtf .
424 CM225
-
R-C:N UAIH1 ... · ~0
~ R-CH2NH2
nitrile 1° amine
H20 0
DIBAH ... II R-C:N .. R-C-H nitrile akdehyde
!Y~tJ-~J~)JDmiJJ.
VC:N LiAIH4 ... H20 VCH2NH2 ~ .
~
benzonitrile phenylmethanamine
Oc=N H~ 0
DIBAH.~ 0" ~ C-H cyclohexanecarbonitrile cyclohexanecarbaldehyde
10.5.3 tJfimu1n1nt~i"l1\1aiLLUUIJstl&i"uu (Hofmann rearrangement)
a:111ltJ~11nDn1tJ1iffit.nnulu,ij1J. ~1aflaa11J.LlJ.ft11a::a1u NaOH 'Vl1a KOH L1J.J1 ... 'U w
.. • ... - ~ .1 .. " ... I .. ... --.. I iJ ., ., ., ., •• ~ .. " 0 LnfllllJn1U1'YlTI1 LV\Lft'lJ'V\~fl111.1EllJ.a LlJL lJ.fJ11lJB,Ufl 'BBBU LLa::a: '1/fJ~nLlJalJ\h~ 1 D: "" ..( ... .. " 1/U 'JJ~llfl111JEllJ.lJ.ElUa~ 1 El::flElll
0 II
R-C-NH2
.!i.1fJ.~J~):Ilim!JJ.
CM225
JJN~ 3-methylpentanamide
0 II
()'C'NH2 N nicotinamide
X2, NaOH
2-methylbutan-1-amlne
()NH2
pyridin-3-amine
4:25
-
ni 'UQ'" n"Jfl l -n ai'" l '"l111Touu~::,r ,,r ouLil "n"Jfll'll u11 Lil ouft'1ou1.h::n au i1ti ty-n £N~1l11 Lftn ft 'I ' 'I
n1t1a::Dl'" LwtJl ntf Uft:: ltJ~il-u (i1,Ya 13.3) Liloun1flfnfuan~iinLLft::a'twufa~~11flL'U ln11J'Jf1tl
· n1flua~nnl-uJ,illtnU'Jflti';l1nm1~Jin ~'1an11aan'Bltuf,a~1uaa t1i'Lilouf11n1 - "'
~ ~- t., ... ~ ... ... ft::ft1U n"n1fiUE1""Dt7nLLft:: acetic anhydride 'JfLfi1U1Jft11L1'1::fi1J£lfl«1~n11ll~ft1U'Jf'Ufl . 'I
1fiULQ'r41::LaRL'naf-na"nfi1LL£l~fln L,.'U l1faaTstrua'ilnfl, vinyl acetate monomer (VCM), . v
,ansuald'n" uft:: l1i'Lfl1uliLLawlw;-u Liloutl'-u
n1fl ~naflain (glycolic acid) ~1a hydroxyacetic acid .wuLanll'aul-uel'au i1~nn1fl aJouLLft::~ft lmj-u Cl LiJoun1fiUDBJ\h ~11fl1Dn9 (a-hydroxy acid ~1a AHA) 111LftnftLan~Rfl
'I J 'I 'I
lin,"n11LLwnuuft::~iiflnm-ti'i'nM-1~1 ';l'Ui)"~iiflnmttfn1fl11llw::a1fl1::iuaflft1~n11ll 'I
n1fiE1~~wn (adipic acidl lin1louft,£l'U 66, n1f1Vit77Tu6n (butanoic acid) LLft::n1fl
urn'111Tu6n (hexanoic acid) LiJ'Ui1L~ni~louLiiflu11::ti1U, n1fl111in (malic acid) Ufl::n1t1 inm (citric acid) wul-u~n~ftlli~~1u'Jf\tfl ilft'1oun1L~1RLtAU1
0 1)- .q HXCOOH HOOCXH H~OH HO·· O OH OH 0 0 H COOH H COOH 0
malic acid citric acid maleic acid fumaric acid malefc anhydride
111lBDnuau~IJ~f11l (maleic anhydride), n1fl111lf1Dn (maleic acid) ua::n1flrl111 v
1n (fumaric acid) utift:: 1uLftnath"il~lifl'1fuaila 2 \1\li ua::~-un-::fi1::\'\11"i'" ~nlaDn 'I "' "' "'
uau~JJ~fl1mLft:n1fl111lfiDn Ltlou~flqilutuitylou~flfti\'\n11liL1'Bou'Jfilflfi1" 'J L,.ou l'fiuuaa flfl, L'fiU'WE1RlE1tflt1E1f. ~fl&n~nnll'r4£lRLllllf UR:fti1LflJj't11"n11Ln~1
n1flrl1111n LiJ~la 1'lfLll£lfLt"LT!J1flmfl,£l"n1flli1LR~n W1JL'U~'Jf\'\ft1U'Jfilfll-Kl~ v '
1R'LtJi'U1L 'U£l1~11LLR:Lfl1fl"~ll LfJ'ULn1L;'-Itl'U L 'U011't11l 1iu 'WBilDBl t7.D-flli~lltl1 \1\iin LL~"L;1 ,f'1li'ULflftfl1JL"1 LLR::LiLtt1Ull01tlfl:;1ilouuaft'J'nfin
~ua1iu (niacin) ~;a itt1iluil-a Li1oun1flfl1fuan•iin'Jfilttua11ulliln, ua-ulaao-u
';l1nn1fl ~wpn (pyruvic ackt) LfJU&n1t"lti'lllun1:tJ1Un1nn"t1Lflii ltl'';l1nn11RR1Un~ lflw LLft:n1flfflin (cholic acid) LiJUn1fl,{1fim-3(U~tl1Jt1nfl8U9W't781Bfi
426 CM225
-
~COOH
ll&.~ N
nicotinic acid (niacin)
0
'a~ methyl butyrate
iut.J:1fl
pyruvic acid ·
0
'-../'a~ propyl acetate
(pear)
COOH
cholic acid
0
yo~ IY isobutyr' propionate isopentyl acetate
(rum) na'lu
0
~0~ octyl acetate
ill
0
~0~ 0
CM225
benzyl acetate (peach)
isopentyl pentanoate (apple)
~0/ UNH2
methyl 2-aminobenzoate f)~"
0
~0/ UOH me.thylsalicylate
u1iu1:ri1
427
-
428
Cefaclor (antibiotic)
OH 0 CH3CH2 :
Camptothecin
m ~ .. "vv ll"" vnn 10
.il
Fumimycln
Oaeltamivir
CM225
-
(3) CH3CH2-0-CH2CH3
5. 1fl'l\1rn"Lflfl£lUfJiflUDU ~~~~fl1l
Go (1) 0
0
0
(2) Co Go
(4) 0
0 II
(2) H-C-OCH2CH3
0 . II
(4) CH3-C-OH
0 0
~0~ (2)v
0 0
(4)~
0 0
(3) Cro (4)~0~ • 7. Lactam flO .•...
( 1) cyclic acids
(3) cyclic amines .
(5) cyclic amides
8. Lactone ti a ..... . (1) cyclic acids
CM225
(2) cyclic esters
( 4) cyclic anhydrides
(2) cyclic esters
429
-
(3) cyclic amines
(5) cyclic amides
(4) cyclic anhydrides
9. fa IUPAC 1JB~ft'11tialt.Jif fia .....
Rei ( 1) 2-hydroxy-3-bromo-4-ethylhep.nyl chloride
(2) 3-bromo-4-ethyl-2-hydroxyhept~noyl chloride
(3) 3-bromo-4-ethyl-2-hydroxyhept~noic acid . (4) 3-bromo-2-hydroxy-4-propylhe~anoyl chloride
10.lfl1~rn~\tlfiB ethyl p-hydroxyben~oate
430
(1)
..........,o0...,.o OH '~ j
0~ (3) ~. OH
I
(2) ~OH _r[ O'U
(4) · ~ OH
11. cyclopentyl cyclohexanecarboxylat• fiaia\tl
·(1)do ca>oJ-oD
12. lfl,~rn~tialt.Jd'ia ..... 0 II
6~HCH2CH3
(1) 1-ethylbenzamide
(3) N-ethylbenzamide
(2) do' .(4) cfoD
(2) ethylaminobenzoic acid
· (4) ~,N-dlmethylbenzamide
CM225
-
13. 811 \t1ti a N-ethylacetamide
.~NH2
(1) 0
0 0 )l)(__
(2) ~ l ~Ny
(4) 0
(1)15 (2)7 (3)5 (4)8
15. ~Btl1li1::1J1J IUPAC ,.8~811\\Lia 14 fia ..... ( 1) phenylmetnyl-2,4,4-trimethylpentanoate
(2) benzyl 2-methyl-4,4-dimethylpentanoate
(3) benzyl 2,4,4-trimethylpentanoate
(4) benzyl. 2,4,4-trimethylbutanoate
16. ~Btl1li1::1J1J IUPAC ,.a~~U~r11Rfla ..... . &N v
(1) benzyl nitrile (2) phenyl cyanide
(3) benzene cyanide (4) benzonitrile
17. 811\tltialtlii'Lntl~\L1J::lllltl1L~\Ln1JJ} LLtilliLfifln1J81T!fUtlLfl!J1n\LLB~ (1) CH3CH20CH2CHa
(2) CH3CH2COOH
(3) (CH3CH2hCHOH
(4) CH3CH2NHCH2CH3 --~ ..1 ..e.... ... ... tl I "tl.r 18. 11htlfiLV\ll1::~ tV\11Jn11Ltl1Ull811 1::naut1a L '"
0
~CI (1) hexanal + Cl2, LLR~ (2) 1 ;-ehlorohex~ne + Cr03
(3) hexanoic acid+ SOCI2 (4) hexanoic acid anhydride + cf
CM225 431
-
... ..1 1 .., .. .. ~- -~ .. . • .. .. 19. UJ£1 Ltlrt Z L14£l14Yi141MJEI-3n1tlfl1'1lJOO"Dftn R-C(O)Z Ln1JLfttUJ1111WJJEI-3'V\1Jfl111J014ft
. • v
(1) L~O Z iiR111Yil~Yl1ft1Jft-3111n v
(2) L~Oti1ftti1Yil~ff1R1J1JEI-3 Z \taf,J 20. d1tl1Jfl1111l1fiat.J~ffiu1n11LLrt14fiA'Vl~L£l•ft1Ja~&n1t.l7:n£Jufialt.Jd' Liluath"l'
0 0 0 0 0 II II II II II
CH3-C-CI CH3-c-0pH3 CH3-C-NH2 CH3-C-O-C-CH3
(A)
(1) A 1¥B > C > 0
(2) C > 8 >/ 0 > A
(3) D > 8 >'A> C
(4) A> 0 > 8 > C
(B) (C) (D)
,. ···- ,. 1 ,. .- • L.... T • ..lf~t • ..1 • 21. fl1111 L11J£jfl1U1fl11 Lll tl1 Lfttn11ffC9UUt'U187110-3n1tlL1J14L'lf£lnrtiJ'V\~LLftUftfl1" ')
432
(Y) ~tl1LL'V\U-3W111 L14ft1111:L1JftLfJ11.L~ULtl 0 II
QOCH~ Ho-
y
• (1) Lll a Y = N02 > 8r > H > CH3 > OCH3 . ' . (2) LliD Y =·OCH3 > N02 > Br > H > CH3
• (3) LlJD Y = OCH3 > CH3 > H > Br;. N02 • (4) LliD Y = H > OCH3 > CH3 >,Br > N02
22. L14rt1""'"i1llntJn11ltrltl1latfLamrtafL~oiin1tlLil:Uti1Li-3 L14fttl11:~iiLuft ..... (1) Lu14t.l~ffiu1-uittlrt114nau (2) Li1utl~ffiu1llirt1unau
(3) lliLnt1t.J~ffiu1 (4) t.l~ffitJ1Lntlu1nn11 23.1LDL~uf1fl\,jl14n"l1Lt.Jau\ULUft-3&n1tiQltJtff1a'Ji£lLfl
0 0
d'o~ (1) H2so ... so3
(3) H20
0
? '" d'OH (2) NH3 .
(4) 1. LiAIH4, ether 2~ H20
CM225
-
24. ft1iufl11ll1eJ~l1tieJtJ~ffiv1n~ti',,e~eJ"t~"lfueJ~n,"fl1fueJn'BanLiJl.I.LLuuifl (1) acid halide > ester > acid anhydride > amide
(2) acid anhydride > amide > acid halide > ester
(3) amide> ester> acid anhydride/> acid halide
(4) acid halide > acid anhydride >ester> amide.
25. ti'T;J:Ltla u1.1.! u !n1miJl.l.n1tlfl1futn'Ban ';1: i -Ktl~mt11 '" ( 1 ) oxidation
(3) dehydration
(5) addition
(2) reduction
(4) hydrolysis
... wtil-r .. -- n 26. LEJWL 'YIEJ191El L \l.ll1';11nn1tlfl111Jeln'1JanLLa:LLeJSneJDElft tl
1. HBr, peroxide
2. Mg, ether
3.C02
4. H3o+, 5. SOCI2, pyridine
o (Yoy )lo~ o
(YCOOH
(2) HOOC~ . ~OH · (YCOOH
(4) HOA_/ )__OH
?
(1) carboxylic acid (2) Grignard reagent
(3) acid chloride (4) alkyl halide
28. ~afl~a'V\sn-;J1n.tl~ffiu1tialtJd' flEJW11Lfl
CM225
KMn04~0H fi111Jfau
SOCb .. CH3CH20H .. ?
433
-
(1) acetaldehyde
(3) acetyl chloride
(2) acetic acid
(4) acetamide
30 ... tl~mu1tioltJdfl11ltl'Nifl~alfl
'11 CCOH I ~ ~CI + I 'A pyridine
(1). I ~, () C2l yJo~ · ~
(3) ltl'lf-3 1 ua: 2
31. tJ~rnu,fioltJdi.tl'R1'''" 0 II
CH3-CH2-C-OH + CH3-180H ?
18~ ~ . (1) CH3-CH2-c-OCH3 (2) CH3-CH2-C-
18.0CH3
18~ ~ (3) CH3-CH2-C-
180CH3 (4) CH3-CH2-c-OCH3
32. L~o lu Lfl1laLfLoRL noftio ltJd'~:ltl'Nifl~afl1a.J'Jio '" 0 II
CH3CH2CH2C-OCH2CH3
(1) propanoic acid ua: propan-1-ol (2) butanoic acid ua:: ethanol (3) ethanoic .acid ua:: butan-1-ol (4) propanoic acid ua: ethanol
33. o:l2Jtl~Lfifl~1nn1fiL1J~L'JJDnnu CH3CH2NH2 flO
'--'~00 ,~
(1) A
0
HN~
.(3)6
434 CM225
-
34. tJ~ffiU1tl El 'tJ\i' \LT;J: \ TiL£JL1Utffe \tt 0
cY~/ ... (1) 1. NaBH4 ; 2. H30+ (2). H2N-NH2/KOH (Wolff ... Kishner reduction)
(3) 1. BHafTHF ; 2. H30
0 . II
H-C-NHCH2CH3
N-ethylformamide
0
+ + (4) 1. ~iAIH4 ; 2. H30
0 . II G)
(1) H-c-o- Na+ + CH3CH2NH3 II
(2) H-c-o- Na+ + CH3CH3 + NH3
0 II +
(3) H-c-o- Na + CH3CH2NH2
37. tJ~ffiu1fialud\L,1:'ti~afl~alfl vcN cH3CH2MgBr ,..
0
H o• 3 ...
0 II
(4) H-C-OH + . CH3CH2NH2
(1)~ (3)~ v N,OH
(2) ()'("
(4) v~ ........... 38. U~MU1fl £) 'tJd\ ,r,L£) L 1Utli £) '"
(2) H2f'Ni +
(3) 1. DIBAH/toluene ; 2. H30
CM225 435
-
0
~OH ~H d'OH
(1) (2) (3) ... ~
(4) YHl')1lUYh1 1, 2 LLft:: 3 40. ~a~~ft~~n~a~u~n;u,~nlun~oial~
~Jl-~ Ho• V 0 · + CH3MgBr (exc;ess) _____.... 3 ..
(3) ft11~nlud tin 3-methylbutanoyl2-methylbutanoate.
DU . 0. . .
••••••••••••••••••••••••••••••••••••••••••••••• 'II ••••••••••••••••.••••••••••••••••••••••••.••
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -. ........................................ .
436 CM·225